EP1292636A1 - Infusion of dye using a plasticizer - Google Patents

Infusion of dye using a plasticizer

Info

Publication number
EP1292636A1
EP1292636A1 EP01928379A EP01928379A EP1292636A1 EP 1292636 A1 EP1292636 A1 EP 1292636A1 EP 01928379 A EP01928379 A EP 01928379A EP 01928379 A EP01928379 A EP 01928379A EP 1292636 A1 EP1292636 A1 EP 1292636A1
Authority
EP
European Patent Office
Prior art keywords
article
plastic material
dyes
solvent
dye
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01928379A
Other languages
German (de)
French (fr)
Other versions
EP1292636B1 (en
Inventor
Paresh V. Kitchloo
Robert A. Sallavanti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gentex Optics Inc
Original Assignee
Gentex Optics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gentex Optics Inc filed Critical Gentex Optics Inc
Publication of EP1292636A1 publication Critical patent/EP1292636A1/en
Application granted granted Critical
Publication of EP1292636B1 publication Critical patent/EP1292636B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/928—Solvents other than hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0004—General aspects of dyeing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65125—Compounds containing ester groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/922—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents hydrocarbons
    • D06P1/924—Halogenated hydrocarbons
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses

Definitions

  • the invention relates to the infusion of dyes into the surface of an article formed of a plastic material using one or more substances each capable of plasticizing the material. More particularly, it relates to treating the surface of an article formed of a plastic material with a solution comprising one or more solvents each aggressive to said material, one or more dyes, and one or more substances capable of plasticizing the material.
  • thermoplastic which is a condensation product resulting typically from the reaction of bisphenol A derivatives with phosgene.
  • Many dyes degrade at the high molding temperature of polycarbonate. Accordingly it would be advantageous to treat the plastic article after it has been formed.
  • U.S. Patent 4,657,345 to Gordon utilizes aggressive solvents in combination with various heating steps. However, such surface defects as bubbhng, hazing and crazing are caused by retained solvent.
  • U.S. Patent 5,453,100 to Sieloff combines an aggressive solvent with a moderating solvent which acts to dilute and reduce the aggressiveness of the infusing solvent. This approach decreases the volatility of the solvent making it more difficult to drive off, resulting in increased bubble formation at or near the surface of the article.
  • a variant of this approach is to utilize only non-aggressive solvents which reduces solvent penetration and compromises dye density, for example, U.S. Patent 4,043,637 to Hovey, and U.S. Patent 4,323,597 to Olson.
  • Our invention comprises treating the surface of a previously formed
  • the material It is preferable that the material have no plasticizer in it prior to
  • the aggressive solvent enables
  • the plasticizer is thought to provide sufficient polymer mobility to allow the
  • optical transmission characteristics may be incorporated therein to affect the optical transmission characteristics.
  • These dyes may include photochromic dyes, cosmetic tinting dyes, infrared
  • combination of dyes may also be employed, for example, an ultraviolet absorbing
  • photochromic dyes include palatinate purple, sea green, corn yellow and berry
  • a solvent aggressive to the plastic and also capable of dissolving the dye and a plasticizer is selected.
  • An aggressive solvent is one which has a solubihty parameter ⁇ which, according to the theorem of Hildebrand, is within plus or minus 1 of the solubility parameter of the plastic when measured in (cal/cm 3 ) 0 - 5 .
  • Polycarbonate for example has a solubility parameter ⁇ of 9.8 (cal/cm 3 ) 0 5 .
  • the aggressive nature of the solvent allows the dye to penetrate to a sufficient depth of 75 to 150 microns below the surface of the article, enabhng good dye density.
  • a combination of aggressive solvents may be used.
  • the use of non-aggressive solvents is disadvantageous because they do not provide sufficient dye penetration and further may be difficult to drive off.
  • acetone has a solubility parameter of 9.9, its use should be avoided, since it is too volatile and causes crystallization of polycarbonate. Further, dodecanol-1, having a solubility parameter of 9.8, is not recommended because even higher alcohols are somewhat hydrophilic and tend to absorb water vapor.
  • Plasticizers are sometimes used during manufacturing to give an
  • the infused plasticizer provides local surface mobility to the plastic
  • the plasticizer is polycarbonate, the plasticizer
  • One or more of these plasticizers may be used in combination.
  • the treating solution comprises the aggressive solvent or solvents,
  • plasticizer typically 1% to 4%, or more, by weight of plasticizer dissolved in the solvent and
  • the polycarbonate article is contacted with the solution for at least ten seconds, but generally not more than one minute.
  • a lens In the case of a lens,
  • one or both surfaces of the lens may be coated with the solution or the lens may
  • the article is
  • annealing consisted of heating the article from 85°F to 265°F in four hours and
  • the resulting dyed article is transparent, having a surface layer
  • PMMA polymethyl ethaerylate
  • LEXAN polycarbonate-polyester copolymers
  • PS polystyrene
  • ⁇ 8.56
  • the glass transition temperature of polycarbonate is roughly 152°C, while that of PMMA is 105° C., that of PS is 100°C, and that of PET is 80° C.
  • polycarbonate is the one for which our invention is especially useful, since for the other thermoplastics, there would be reduced dye degradation at the lower molding temperatures. It will further be understood that the maximum annealing temperature in each instance would be reduced to appreciably less than the glass transition temperature.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Eyeglasses (AREA)
  • Coloring (AREA)
  • Medicinal Preparation (AREA)

Abstract

A method of infusing a dye into the surface of an article formed of a plastic material comprises contacting the surface with a solution including one or more solvents each aggressive to the plastic material, one or more dyes and one or more substances each capable of plasticizing the plastic material. If the plastic material is polycarbonate, then the aggressive solvent may be one or more chlorinated hydrocarbons. The dye may be a photochromic dye, a cosmetic tinting dye, dyes for absorbing infrared, laser and ultraviolet radiation, or combinations thereof. A wide range of plasticizers has been investigated. The article is contacted by the solution for ten seconds to one minute; and nearly all the infused solvent is then evaporated from the article by heating. The use of one or more plasticizers reduces or eliminates bubbling or hazing of the contacted surface during solvent evaporation. The dyed article comprises a surface layer having a depth of the order of magnitude of 100 microns containing one or more dyes, one or more plasticizers and, likely, a trace amount of the one or more aggressive solvents.

Description

TITLE OF THE INVENTION
INFUSION OF DYE USING A PLASTICIZER
FIELD OF THE INVENTION
The invention relates to the infusion of dyes into the surface of an article formed of a plastic material using one or more substances each capable of plasticizing the material. More particularly, it relates to treating the surface of an article formed of a plastic material with a solution comprising one or more solvents each aggressive to said material, one or more dyes, and one or more substances capable of plasticizing the material.
BACKGROUND OF THE INVENTION
Attempts have been made to introduce dyes into articles formed of a plastic material. For optical articles such as lenses, a thermoplastic frequently employed is polycarbonate, which is a condensation product resulting typically from the reaction of bisphenol A derivatives with phosgene. Many dyes degrade at the high molding temperature of polycarbonate. Accordingly it would be advantageous to treat the plastic article after it has been formed.
U.S. Patent 4,657,345 to Gordon utilizes aggressive solvents in combination with various heating steps. However, such surface defects as bubbhng, hazing and crazing are caused by retained solvent. U.S. Patent 5,453,100 to Sieloff combines an aggressive solvent with a moderating solvent which acts to dilute and reduce the aggressiveness of the infusing solvent. This approach decreases the volatility of the solvent making it more difficult to drive off, resulting in increased bubble formation at or near the surface of the article. A variant of this approach is to utilize only non-aggressive solvents which reduces solvent penetration and compromises dye density, for example, U.S. Patent 4,043,637 to Hovey, and U.S. Patent 4,323,597 to Olson.
SUMMARY OF THE INVENTION
Our invention comprises treating the surface of a previously formed
article of plastic material with one or more solvents aggressive to the plastic
material having one or more dyes dissolved in the solvent and having further
dissolved in the solvent one or more substances capable of plasticizing the
material. It is preferable that the material have no plasticizer in it prior to
formation of the article, since such would reduce the rigidity, strength and the
mechanical properties of the formed article. The aggressive solvent enables
penetration to depths in excess of 100 microns to achieve excellent dye density.
The plasticizer is thought to provide sufficient polymer mobility to allow the
solvent to almost completely escape during subsequent heating without causing
bubbling, hazing or crazing. The extent of degradation of mechanical surface
properties of the plastic article caused by retained plasticizer is negligible. It is
the object of our invention to prevent bubbling and hazing of the surface of an
article formed of a plastic material into the surface of which has been infused one
or more dyes dissolved in one or more solvents each aggressive to the plastic by
also dissolving in the solution one or more substances each capable of
plasticizing the plastic material. DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the manufacture of optical devices, such as lenses, various dyes
may be incorporated therein to affect the optical transmission characteristics.
These dyes may include photochromic dyes, cosmetic tinting dyes, infrared
absorbing dyes, laser radiation absorbing dyes and ultraviolet absorbing dyes. A
combination of dyes may also be employed, for example, an ultraviolet absorbing
dye to prevent premature deterioration of a photochromic dye. Suitable
photochromic dyes include palatinate purple, sea green, corn yellow and berry
red which may be obtained from James Robinson, Ltd. of Huddersfield, United
Kingdom.
A solvent aggressive to the plastic and also capable of dissolving the dye and a plasticizer is selected. An aggressive solvent is one which has a solubihty parameter δ which, according to the theorem of Hildebrand, is within plus or minus 1 of the solubility parameter of the plastic when measured in (cal/cm3)0-5. Polycarbonate for example has a solubility parameter δ of 9.8 (cal/cm3)0 5. Suitable aggressive solvents for polycarbonate are tetrahydrofuran (C4H8O, δ = 9.1) and chlorinated hydrocarbons, for example, chloroform (CHCI3, δ = 9.3), methylene chloride (CH2CI2, δ = 9.7) and dichlorobenzene (CβHjCla, δ = 10.0). The aggressive nature of the solvent allows the dye to penetrate to a sufficient depth of 75 to 150 microns below the surface of the article, enabhng good dye density. A combination of aggressive solvents may be used. The use of non-aggressive solvents is disadvantageous because they do not provide sufficient dye penetration and further may be difficult to drive off. Although acetone has a solubility parameter of 9.9, its use should be avoided, since it is too volatile and causes crystallization of polycarbonate. Further, dodecanol-1, having a solubility parameter of 9.8, is not recommended because even higher alcohols are somewhat hydrophilic and tend to absorb water vapor.
Plasticizers are sometimes used during manufacturing to give an
otherwise rigid plastic flexibility; but as previously indicated we prefer that the
plastic have no plasticizer prior to formation of the article. In the present
application, the infused plasticizer provides local surface mobility to the plastic
matrix, allowing the deeply penetrating solvent to almost completely evaporate
during subsequent heating. Where the plastic is polycarbonate, the plasticizer
may be selected from the following table which includes both acid and alcohol
moieties. Table 1 - Listing of Acceptable Plasticizers
One or more of these plasticizers may be used in combination.
The plasticizers sold under the trademark BENZOFLEX® may be obtained
from Velsicol Chemical Corporation of Rosemont, Illinois.
The treating solution comprises the aggressive solvent or solvents,
typically 1% to 4%, or more, by weight of plasticizer dissolved in the solvent and
a conventional quantity of dye dissolved in the solvent. As a general rule, it is
preferable to use the minimum concentration of plasticizer necessary to achieve
the desired result. The polycarbonate article is contacted with the solution for at least ten seconds, but generally not more than one minute. In the case of a lens,
one or both surfaces of the lens may be coated with the solution or the lens may
be completely immersed in the solution. In the case of immersion, the article is
removed from the solution at a uniform withdrawal rate. The solvent is then
evaporated from the surface layer of the article by annealing. In practice,
annealing consisted of heating the article from 85°F to 265°F in four hours and
then cooling the article from 265°F to 85°F in one hour. It will be appreciated
that the maximum temperature is appreciably less than the glass transition
temperature of polycarbonate of 305°F. = 152°C.
The resulting dyed article is transparent, having a surface layer
with a depth of the order of 75 to 150 microns, which contains the infused dye
and plasticizer and, likely, trace amounts of retained solvent, which in larger
amounts would cause bubbling, hazing or crazing.
When polycarbonate lenses were contacted with chloroform
containing no plasticizer, the lenses became hazy and developed bubbles after
annealing.
A lens contacted with chloroform containing 1% of either of the BENZOFLEX® plasticizers had some bubbling and hazing after annealing.
Increasing the concentration of plasticizer to 4% provided undetectable bubbling
and haze after annealing. The remaining plasticizers caused no haze at 1%
concentrations and no bubbling at 4% concentrations. The results of tests appear
in the following table. It will be understood that a 4% plasticizer concentration
may be achieved by combining any four of the above plasticizers in 1%
concentrations each.
Plastics other than polycarbonate would include polymethyl ethaerylate (PMMA), δ = 9.09, and polycarbonate-polyester copolymers (LEXAN), for which the foregoing solvents and plasticizers would be suitable, polystyrene (PS), δ = 8.56, for which carbon tetrachloride, δ = 8.6, methyl isopropyl ketone, δ = 8.5, and propyl propionate, δ = 8.5, would be suitable solvents and for which the foregoing phthalate plasticizers would be suitable, and polyethylene terephthalate (PET), δ = 9.5, for which chlorobenzene, δ = 9.5, and chlorostyrene, δ = 9.5, would be suitable solvents and for which the foregoing phthalate plasticizers would be suitable. The glass transition temperature of polycarbonate is roughly 152°C, while that of PMMA is 105° C., that of PS is 100°C, and that of PET is 80° C. Of these thermoplastics, polycarbonate is the one for which our invention is especially useful, since for the other thermoplastics, there would be reduced dye degradation at the lower molding temperatures. It will further be understood that the maximum annealing temperature in each instance would be reduced to appreciably less than the glass transition temperature.
It will be seen that we have accomplished the object of our invention. We have prevented bubbling and hazing of the surface of an article formed of a plastic material into which has been infused a dye dissolved in a solvent aggressive to the plastic. This advantageous result is achieved by also dissolving in the solvent one or more substances each capable of plasticizing the material.
It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of our claims. It is further obvious that various changes may be made in details within the scope of our claims without departing from the spirit of our invention. It is, therefore, to be understood that our invention is not to be limited to the specific details shown and described.
Having thus described our invention, what we claim is:

Claims

THE CLAIMS
1. In a method of infusing a dye into the surface of an article formed of a plastic material, wherein the surface of the plastic article is contacted with a solution comprising one or more dyes dissolved in one or more solvents each aggressive to the plastic material and wherein the article is subsequently heated to evaporate the solvent or solvents, the step comprising dissolving in the solvent or solvents prior to contacting the surface of the article one or more substances each capable of plasticizing the plastic material.
2. The method of Claim 1, wherein each solvent has a solubility parameter measured in (cal/cm3)0-5 which is within plus or minus unity of that of the plastic material.
3. The method of Claim 1, wherein the solution is devoid of a solvent non-aggressive to the plastic material.
4. The method of Claim 1, wherein the solution contains at least 1% by weight of said substance or substances.
5. The method of Claim 1, wherein the dye is selected from the group consisting of photochromic dyes, cosmetic tinting dyes, infrared absorbing dyes, laser radiation absorbing dyes, ultraviolet absorbing dyes, and combinations thereof.
6. The method of Claim 1, wherein the article, prior to contact with the solution, contains no substance capable of plasticizing the material.
7. The method of Claim 1, wherein the article is immersed in the solution.
8. The method of Claim 1, wherein said surface is contacted for at least 10 seconds.
9. The method of Claim 1, wherein said surface is contacted for not more than one minute.
10. The method of Claim 1, wherein the article is heated during a first time interval from a first temperature to a second elevated temperature, less than the glass transition temperature of the plastic material, and then cooled during a second time interval shorter than said first time interval from the second elevated temperature to the first temperature.
11. A dyed article including in combination an article formed of a plastic material having a surface layer with a depth of the order of magnitude of 75 to 150 microns, said surface layer being infused with significant amounts of one or more dyes and one or more substances each capable of plasticizing the plastic material.
12. An article as in Claim 11 wherein the surface layer contains a trace amount of one or more solvents each aggressive to the plastic material.
13. The article of Claim 11, wherein the dye is selected from the group consisting of photochromic dyes, cosmetic tinting dyes, infrared absorbing dyes, laser radiation absorbing dyes, ultraviolet absorbing dyes, and combinations thereof.
14. An article, as in Claim 11 wherein the article contains no substance capable of plasticizing the material other than in said surface layer.
15. An article as in Claim 12 wherein each solvent has a solubility parameter measured in (cal/cm3)0-5 which is within plus or minus unity of that of the plastic material.
16. An article as in Claim 12 wherein the surface layer is devoid of a solvent non-aggressive to the plastic material.
EP01928379A 2000-04-11 2001-04-09 Infusion of dye using a plasticizer Expired - Lifetime EP1292636B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US547088 2000-04-11
US09/547,088 US6719812B1 (en) 2000-04-11 2000-04-11 Infusion of dye using a plasticizer
PCT/US2001/011259 WO2001077212A1 (en) 2000-04-11 2001-04-09 Infusion of dye using a plasticizer

Publications (2)

Publication Number Publication Date
EP1292636A1 true EP1292636A1 (en) 2003-03-19
EP1292636B1 EP1292636B1 (en) 2006-03-08

Family

ID=24183299

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01928379A Expired - Lifetime EP1292636B1 (en) 2000-04-11 2001-04-09 Infusion of dye using a plasticizer

Country Status (9)

Country Link
US (1) US6719812B1 (en)
EP (1) EP1292636B1 (en)
JP (1) JP3753660B2 (en)
AT (1) ATE319765T1 (en)
AU (2) AU5524301A (en)
BR (1) BR0110035B1 (en)
DE (1) DE60117775T2 (en)
ES (1) ES2254406T3 (en)
WO (1) WO2001077212A1 (en)

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Publication number Publication date
AU2001255243B2 (en) 2006-05-25
BR0110035B1 (en) 2012-01-10
ATE319765T1 (en) 2006-03-15
WO2001077212A1 (en) 2001-10-18
US6719812B1 (en) 2004-04-13
AU5524301A (en) 2001-10-23
DE60117775D1 (en) 2006-05-04
JP3753660B2 (en) 2006-03-08
DE60117775T2 (en) 2006-09-07
EP1292636B1 (en) 2006-03-08
JP2003530450A (en) 2003-10-14
BR0110035A (en) 2003-05-27
WO2001077212B1 (en) 2002-01-03
ES2254406T3 (en) 2006-06-16

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